Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C335/00—Thioureas, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
  • C07C335/04—Derivatives of thiourea
  • C07C335/16—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
  • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
  • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
  • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
  • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
  • A01N47/30—Derivatives containing the group >N—CO—N aryl or >N—CS—N—aryl
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
  • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
  • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
  • A01N47/32—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing >N—CO—N< or >N—CS—N< groups directly attached to a cycloaliphatic ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
  • C07C275/26—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of rings other than six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
  • C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
  • C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
  • C07C275/32—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by singly-bound oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
  • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
  • C07C323/24—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
  • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/14—The ring being saturated

Definitions

• the present invention relates to new (thio) ureas, a process for their preparation, intermediates therefor and their use as crop protection agents.
• Heavy metal salts of ethylene bisdithiocarbamic acid in particular their zinc salts, have long been used in crop protection for combating phytopathogenic fungi (cf. R. Wegler, Chemistry of Plant Protection and Pest Control, Vol. 2, 565, Springer-Verlag, Berlin, Heidelberg, New York 1970). However, their effect is not always entirely satisfactory at low application rates and concentrations.
• the new (thio) ureas of the formula (I) have strong fungicidal properties. Compared to the state of the art, they show a better effectiveness, especially at low application rates and concentrations.
• the aryl radicals of the radicals R 2 and Ar can, independently of one another, preferably have substituents, for example halogen such as fluorine, chlorine and bromine, C 1 -C 4 -alkyl such as methyl and ethyl, haloalkyl having 1 to 2 C atoms and 3 to 5 halogens such as fluorine and chlorine and haloalkoxy and halothioalkoxy, each having 1 to 2 carbon atoms and up to 5 halogens such as fluorine and / or chlorine.
• substituents for example halogen such as fluorine, chlorine and bromine, C 1 -C 4 -alkyl such as methyl and ethyl, haloalkyl having 1 to 2 C atoms and 3 to 5 halogens such as fluorine and chlorine and haloalkoxy and halothioalkoxy, each having 1 to 2 carbon atoms and up to 5 halogens such as fluorine and /
• the phenyl radicals of the radicals R 2 and Ar can independently of one another, particularly preferably, substituents, for example fluorine, alkyl such as methyl and ethyl, Haloalkyl such as trifluoromethyl and haloalkoxy and halothioalkoxy such as trifluoromethoxy, 1-difluoro-2-fluoro-2-chloroethoxy or trifluoromethylthio.
• substituents for example fluorine, alkyl such as methyl and ethyl, Haloalkyl such as trifluoromethyl and haloalkoxy and halothioalkoxy such as trifluoromethoxy, 1-difluoro-2-fluoro-2-chloroethoxy or trifluoromethylthio.
• the secondary amines and (thio) isocyanates used in carrying out the reaction according to the invention are generally defined by formula (II) and formula (III).
• the radicals A r, R 2 and R 1 have the meanings which have already been mentioned preferably and particularly preferably for these radicals in connection with the description of the substances of the formula (I) according to the invention.
• the secondary amines of the formula (II) used in the process according to the invention are new. Their manufacture is described below.
• the isocyanates of the formula (III) used are generally known compounds.
• reaction can be carried out without a diluent.
• Reaction is preferably carried out in a diluent.
• Inert organic solvents for example ethers such as dioxane, hydrocarbons such as cyclohexane, aromatic hydrocarbons such as benzene and toluene, chlorinated hydrocarbons such as chloroform and nitriles such as acetonitrile can be used as diluents.
• ethers such as dioxane
• hydrocarbons such as cyclohexane
• aromatic hydrocarbons such as benzene and toluene
• chlorinated hydrocarbons such as chloroform
• nitriles such as acetonitrile
• the reaction according to the invention is carried out at a temperature of from -20 to 150 ° C., preferably from 0 to 100 ° C.
• reaction temperature is above the boiling point of the solvent used
• reaction can be carried out under elevated pressure up to about 20 bar.
• the reaction is preferably carried out at normal pressure.
• the secondary amines of the formula (II) used in the process according to the invention are new. They are prepared by hydrogenating aldimines of the formula (IV).
• reaction scheme If, for example, 4-fluorobenzaldehyde-cyclopentylimine and sodium borohydride are used as starting materials, the reaction can be represented by the following reaction scheme:
• the aldimines of the formula (IV) used in the preparation of the secondary amines of the formula (II) are new.
• the radicals R 1 and Ar have the meanings which were preferably and particularly preferably mentioned for these radicals in the description of the substances of the formula (I) according to the invention. Their manufacture is described below.
• complex metal hydrides for example lithium alanate, sodium borohydride and cobalt carbonyl hydrogen, particularly preferably sodium borohydride, are preferably used as the hydrogenating agent.
• about 1 mole of hydrogenating agent is used per mole of aldimine of the formula (IV).
• Suitable diluents are preferably alcohols, for example aliphatic alcohols such as ethanol, n-propanol, iso-propanol, n-butanol, particularly preferably methanol.
• the reaction is carried out at a temperature of from -20 to 60 ° C., preferably from -10 to 40 ° C.
• the reaction is carried out, for example, as follows:
• the hydrogenation agent and the alcohol are initially introduced.
• the aldimine of the formula (IV) is added dropwise with ice cooling.
• the mixture is then stirred at room temperature for about 1.5 hours. Now about the same amount of water as alcohol used is slowly added. It is then extracted in the usual way with a chlorinated hydrocarbon.
• the secondary amines of the formula (II) can be isolated by distillation and / or crystallization.
• the aldehydes of the formula (V) and amines of the formula (VI) used in the preparation of the aldimines of the formula (IV) are generally defined by the formulas (V) and (VI).
• the radicals Ar and R 1 have the meanings which have already been mentioned preferably and particularly preferably for these radicals in connection with the description of the substances of the formula (I) according to the invention.
• aldehydes of the formula (V) and amines of the formula (VI) used are generally known compounds.
• the reaction of the aldehydes of the formula (V) with the amines of the formula (VI) can preferably be carried out in a diluent.
• Chlorinated hydrocarbons for example chloroform and dichloromethane, are preferably used.
• the reaction is carried out at a temperature from 0 to 100 ° C., preferably at 20 to 50 ° C.
• the active compounds according to the invention have a strong microbicidal action and can be used practically to control unwanted microorganisms.
• the active ingredients are suitable for use as pesticides.
• Fungicidal agents in crop protection are used to control Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.
• the active ingredients can be in the usual formulations are transferred, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, active ingredient-impregnated natural and synthetic substances, very fine encapsulations in polymeric substances and in coating compositions for seeds, and also in formulations with fuel sets, such as smoking cartridges and cans , spirals and the like, as well as ULV cold and warm fog formulations.
• formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents . If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents.
• extenders that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents .
• surface-active agents that is to say emulsifiers and / or dispersants and / or foam-generating agents.
• organic solvents can, for example, also be used as auxiliary solvents.
• liquid solvents aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylene or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water;
• Liquefied gaseous extenders or carriers mean liquids which are at normal temperature and are gaseous under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide;
• Solid carrier materials are suitable: for example natural rock powder
• Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular and latex-shaped polymers, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.
• Dyes such as inorganic pigments, for example iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
• the formulations generally contain between 0.1 and 95 percent by weight of active compounds, preferably between 0.5 and 90%.
• the active compounds according to the invention can be present in the formulations or in the various use forms in a mixture with other known active compounds.
• active compounds are such as fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, bird repellants, growth agents, plant nutrients and soil conditioners.
• the active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. They are used in the usual way, e.g. by pouring, dipping, spraying, spraying, atomizing, evaporating, injecting, slurrying, spreading, dusting, scattering, dry pickling, wet pickling, wet pickling, slurry pickling or incrusting.
• the active compound concentrations in the use forms can be varied within a substantial range. They are generally mean between 1 and 0.0001% by weight, preferably between 0.5 and 0.001%.
• amounts of active ingredient of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.
• active ingredient concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02%, are required at the site of action.
• Solvent 12.5 parts by weight.
• Acetone emulsifier 0.3 part by weight of alkylaryl polyglycol ether
• active compound 1 part by weight of active compound is mixed with the stated amount of solvent and the concentrate is diluted to the desired concentration with water and the stated amount of emulsifier.
• the disease infestation is evaluated 5 to 8 days after the inoculation.

Applications Claiming Priority (2)

Publications (3)

Family

ID=6139591

Family Applications (1)

Country Status (10)

Cited By (4)

Families Citing this family (6)

Citations (13)

Family Cites Families (3)

• 1981
  • 1981-08-19 DE DE19813132690 patent/DE3132690A1/de not_active Withdrawn
• 1982
  • 1982-08-06 PH PH27685A patent/PH20778A/en unknown
  • 1982-08-09 US US06/406,695 patent/US4487783A/en not_active Expired - Fee Related
  • 1982-08-11 EP EP82107261A patent/EP0072528B1/fr not_active Expired
  • 1982-08-11 DE DE8282107261T patent/DE3271151D1/de not_active Expired
  • 1982-08-13 JP JP57139987A patent/JPS5839655A/ja active Pending
  • 1982-08-16 IL IL66555A patent/IL66555A0/xx unknown
  • 1982-08-18 BR BR8204837A patent/BR8204837A/pt unknown
  • 1982-08-18 DK DK371582A patent/DK371582A/da not_active Application Discontinuation
  • 1982-08-18 ZA ZA825996A patent/ZA825996B/xx unknown
  • 1982-08-18 KR KR8203709A patent/KR890000368B1/ko active

Patent Citations (13)

Non-Patent Citations (5)

Also Published As

Similar Documents

Legal Events